Preparation of phosphorus- and sulfur-containing materials



Patented Jan. 9, 1951 UNITED STATES PATENT OFFICE PREPARATION OF PHOSPHORUS- AND SULFUR-CONTAINING MATERIALS Harry J. Andress, Jr., Woodbury, N. J assignor to Snoopy-Vacuum Oil Company, Incorporated, a corporation of New York This invention has to do with a new and novel class of phosphorusand sulfur-containing reaction products obtained by reaction of phosphorus pentasulfide and a hydroxyaromatic compound.

As is well known to those familiar with the art, dithiophosphoric acids are readily prepared by reacting one molar proportion of P285 with four molar proportions of an alcohol or phenol under suitable reaction conditions. These acids, and metal salts thereof, have been used as wetting agents, flotation agents, mineral oil improving agents, etc. prepared as indicated above, are or dark color, are corrosive towards such metals as copper, and tend to decompose, with the evolution of hydrogen sulfide, when heated. Shortcomingssuch as these have restricted their application, particularly to those uses wherein relatively low operating temperatures are involved.

The present invention is predicated upon the discovery of a new and novel class of phosphorusand sulfur-containing reaction products, and metal salts thereof, which are substantially free from the foregoing undesirable characteristics of dithiophosphoric acids. These new reaction products are acidic, contain phosphorus and sulfur, and are obtained by reaction of one molar proportion of P2555 and about two molar proportions of a hydroxyaromatic compound. Metal salts of the acidic reaction products are obtained by reacting a reaction product of the aforesaid type with a suitable metal compound, as described in detail hereinafter.

Examples of the hydroxyaromatic compounds of phenols which may be used in preparing the reaction products contemplated herein are: phenols, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenolresins, methylhydroxy diphenyl, guiacol, alphaand betanaphthol, alphaand betamethyl naphthol, tolyl naphthol, xylyl naphthol, benzyl naphthol, anthranol, phenylmethylnaphthol, phenanthranol, monomethylether of catechol, chlorphenol and the like.

As indicated above by the list of illustrative hydroxyaromatic compounds, such compounds may contain alkyl substituents. Those hydroxyaromatic compounds which contain one or more relatively long-chain alkyl substituents are desirable for use in preparing acidic, phosphorusand sulfur-containing reaction products (and metal salts thereof) characterized by substantial miscibility or solubility in hydrocarbon fractions such as mineral lubricating oil. these alkyl-substituted hydroxyaromatic com- 8 Claims. (01. 260-461) Unfortunately, however, the acids,

In preparing i petroleum wax having a melting point not substantially less than F., a molecular weight or about250 and at least about 20 carbon atoms per molecule. It will be understood from this-description that the term chlorowax" when used herein refers to a material containing one or more chlorine atoms and a relatively high molecular weight alkyl or radical obtained from a hydrocarbon fraction identified as paraifin wax.

By way of illustration, wax-substituted phenol prepared according to the foregoing procedure, in which a quantity of chlorowax containing three atomic proportions of chlorine is reacted with one mol of phenol and in which the chlorowax contains 20 per cent of chlorine will, for brevity herein, be designated as waxphenol (3-20) Parenthetical expressions of the type (AB) are used hereinafter in connection with the alkyl hydroxyaromatic compounds to designate; (A) the number of atomic proportions of chlorine in the chloro-aliphatic material reacted with one mol of hydroxyaromatic compound in the Friedel-Crafts reaction, and (B) the ch10 rine content of the chloroaliphatic material. In the above example A=3 and 13:20. This same designation is also applied hereinafter to acidic, phosphorusand sulfur-containing reaction products, (and metal salts thereof) of this invention.

Although any of the catalysts of the group known in the art as Friedel-Crafts catalysts may be used in preparing alkyl-substituted hydroxy. aromatic compounds for the purposes of this invention, aluminum chloride is preferred. In this. connection when an alkyl-substituted hydroxyaromatic compound is prepared by a Friedel- Crafts synthesis, the reaction mixture obtained by reacting an alkyl halide and a hydroxyaromatic compound in the presence of a catalyst such as aluminum chloride, the reaction mixture may be reacted directly-without isolating the alkyl substituted hydroxyaromatic compound-.-- with P285 in the ratio of two molar proportions of hydroxyaromatic compound present in the alkyl- Preference is given such as a high molecular weight olefin, and a hydroxyaromatic compoundin the presence of a condensation agent such as sulfuric acid, zinc chloride or the like.

In reacting PzSs with a hydroxyaromatic compound in the proportions indicated above, elevated temperatures are used. Generaly, tem peratures from about 100 C. to about 200 C. provide satisfactory results with reaction tem peratures of about 175 C. being preferred. The reaction may be carried out in the absence of ar'l'inert diluent, although if it is preferred, an inert diluent such as tetrachloroethane, kerosene, Stoddards solvent, mineral lubricating oil fractiqns and the like may be used. When tetrachloroethane, kerosene or other relatively low boiling diluents are used, they may be readily removedfrom the reaction mixture disti lation. The use of a relatively high boiling diluent such as a mineral lubricating oil fraction provides alcon'venient means for obtaining mineral oil concentrates of the desirable reaction product, the oil being'retained with the reaction product rather than separated therefrom by fractionabln It has also been found that further improvement in color and stability of the reaction products can be obtained by treating the P235 reaction mixture with a small amount of finely divided zinc, such as zinc dust. The amount of zinc used is reatively small, as from about 1 per cent toabout 2 per cent, and preferably about two'p'er cent, based upon the quantity of the alkylated hydroxyaromatic compound used in the reaction. Accompanying the finely divided zinc is a small amount of water about The Piss'reaction product, zinc and water, are stirred together, generally at about 100 C. for fifteen to twenty minutes. Water is removed thereafter by heating the mixture at about 110 C. and the water-free mixture is fi tered. through a suitable filter medium to obta n the final reaction product.

Metal salts of the above-described acidic, phOsphorrisand sulfur-containing reaction products are also contemplated herein, and can beprepared by any of the we l-known procedures forma'king metal salts of organic acids. example, the sodium salt may be prepared by reacting said acidic reaction product with a sodium alcoholate and thereafter distilling off the alcohol. Other metal salts can be prepared from the sodium salt by metathesis with a suitable metal compound such as halide, as indicated above. When a substantial y inert d luent is used the reaction of P235 and a hydrcxyaromatic compound, the diluent may be removed prior to the formation of a metal salt or may be removed after-the metal salt has been formed. Also, a mineral lubricating oil concentrate or blend containing a metal salt of the foregoing acidic reaction product may be prepared by using a mineral lubricating oil as the diluent and retainingthe same with the. reaction producti The inetals contemplated herein may be broad- For , chloride.

1y classified as metals of the groups I through VIII of the periodic system. These metals comprise the following: The alkali metals lithium, sodium, potassium, rubidium and caesium; the alkaline earth metals beryllium,- magnesium, calcium, strontium, and barium; the metals zinc, cadmium, and mercury, scandium, lanthanum, aluminum, gallium, indium, thallium, titanium, zirconium, cerium, thorium; germanium, tin and lead; vanadium, columbium and tantalum; arsenic, antimony and bismuth; chromium, molybdenum, tungsten and uranium, rhenium, manganese, iron, cobalt and nickel; ruthenium, rhodium, palladium; osmium, iridium and piatinum.

Some of the rare earth metals are mentioned in the foregoing passage. Other rare earth metals suitable for formation of dithiophosphoric acid s'ats' are those now commercially available as the cerium and yttrium group namely, a mixture of praseodymiuin, neodymium, Samarium, europium, gadolinium, terbium, holmium, erbium, thallium and lutecium.

Further details in the character of the acidic, phosphorusand sulfur-containing reaction products (and metal salts thereof) of this invent on will be apparent from the following illustrative examples:

EXAMPLE I 126 F. was chlorinated by introducing chlorine gas therein at about 100 C. until 14 per cent by weight of chlorine was adsorbed. One hundred grams of the chlorowax were then mixed with 12.3 grams of phenol and three grams of alum inum chloride were added thereto at about 85 C., at a rate sufficiently slow to avoid excessive foaming caused by the evo ution of hydrogen The reaction temperature was then raised to about 175 C. and the reaction 1. lure was stirred for about one hour at this temperature to complete the reaction. The product at this stage was the aluminum phenate of waxphenol (3-141), containing combined ch or ne.

Two hundred grams of a solvent-refined min-" eral oil having a Saybolt Universal viscosity (S. U. V.) of 15 seconds at 210 F. were added to the aforesaid phenate derivative, followed by the addition of 14.8 grams of Pass. The reaction mixture thus obtained was heated for four hours at 175 C. The reaction with 1 :85 was substantially completed after heating for two hours at this temperature, as indicated by the decrease in the amount of hydrogen su'fide evolved during the reaction, but the reaction mixture was heated for an additional period of two hours to insure completion of the reaction. The reaction mixture was then cooled to about 110 C. and two;

mineral oil. The oil blend contained 1 3 per cent phosphorus, 2.0 per cent su fur, and had a neutralization number (N. N.) of 10.

EXAMPLE II One hundred grams of wax-phenol (314) were diluted With 200 grams of the solvent-re dysprosium,

fined mineral oil described in Example I above and the resultant oil blend was heated toabout 150 C. 14.8 grams of P285 were then added and the reaction mixture thus formed was quickly heated to about 175 C. The reaction mixture was then heated for about four hours at 175 C. After cooling the reaction mixture to about 95 C., five grams of zinc dust and three grams of water were added thereto. The zinc treated reaction mixture was then heated for fifteen to twenty m nutes at about 100 C. The reaction mixture was then filtered through Hi-Flo, and the filtrate therefrom was distilled to a maximum temperature of 150 C. at mms. pressure. The finished product (Product Two) is a one to three blend in mineral oil and has the followine analysis: 1.3 per cent phosphorus, 2.0 per cent sulfur, and neutralization number (N. N.) of 10.0.

EXAMPLE III A reaction product related to Product Two, prepared as describ d in Example II above, was prepared in exactly the same manner as Product Two with the sal ent distinction, however, that a mo ar ratio of four molar proportions of phenol contained in wax-phenol (3-14) to one molar proportion of PzSs was used. This product rodu -t 'Th e-- nta.in d 0.6 per cent hosphorus, 1 per cent sulfur and has a neutraliza EXAMPLE IV A quantity of Product Two was h ated with twenty per cent of barium hydroxide octahydrate, until the water of crystallization and wat r from the react on were distilled out by gradual y ra sins the temp rature. (Product Fo r) was a 1:3 oil blend containing 2.7 per cent barium, 1.3 per cent phosphorus and 2.0 per cent sulfur.

EXAMPLE v A quantity of Product Three was treated with barium hydroxide octahydrate in the same man- The prod ct ner as was Product wo in Example IV. The

such representative mineral oils alone and with blends thereof containing a typical reaction product to various well-known tests is presented hereinbelow. 1

Pope Tns'r -These tests were conducted with a mineral lubricating oil fraction having a Saybolt Uni versal viscosity (S. U. V.) of 67'seconds at 210 F. and an A. S. T. lVLpour point of 20 F. The results for the blank oil and the oil blends are listed below in Table 1:

agents of the present invention in the viscosity index of mineral oils to which they are added is clearly shown by the illustrative data shown in.

Table 2 below:

Table 2 Kinematic Vis. C nc., Improving Agent Per O'nt V. I

by Wt.

None 30.10 4. 77 77.1 Product Two. 1.0 36. 0 55 99.2 (Product Three 1.0 32. 74 5. 11 88.6)

OPERATION Tom The effectiveness of the reaction product contemplated herein in stabilizing motor oils against the deleterious effects of oxidation is indicated by an accelerated test in a one-cylinder Lauson engine operated at an oil temperature of 290 F. and a jacket temperature of 212 F. A motor oil having a Saybolt Universal viscosity (S. U. V.) of 45 seconds at 210 F. was used with and without the addition agents, and the neutralization number (N. N.) and the Saybolt Universal viscosity (S. U. V.) at 210 F. were determined after 36 hours. The results of these tests are tabulated in Table 3 below.

Table 3 Cone.

. Y S. U. V.

Improving Agent Pg; (gll; N. h. at 210 F None 10. 0 12. 71 Product One. 0. 67 1. 3 6. 54 Product Two 1. 0 1. 5 6. 55 (Product Three 1.0 3. 9 7. 66)

AccE'LEeArEn OXIDATION Tns'r An accelerated oxidation test has been used in order to determine the corrosive nature of lubricating oils under simulated operating conditions. The apparatus used consists of a circulating arrangement whereby oil at 325 F. under a pressure of ten pounds per square inch, is sprayed against a standard cadmium-nickel bearing for a period of five or fifteen hours. The amount of oil under constant circulation in the systemis 1,500 ccs. 1n passing through the system, the

oil comes into contact with cast iron, steel, stainless steel, copper and the aforesaid cadmiumnickel bearing, and is also exposed to aeration. The oil used in this test contains a small amount of an accelerator, namely, iron .naphthenate (commercially designated as Nuodex, six per cent F8203) which greatly increases the rate of oxida'-.' tion of the oil. The degree of oxidation suffered by the oil is shown by the development of acidity therein asgmeasured bythe. neutralization number: (N. N.), the loss in weight of the-.cadmium-nickel bearings and the percentageof viscosity increase of the oil. The oil used was a solvent-refined oil having a Saybolt Universal viscosity (S. U. V.) of

tabulated below in Table 6.

lowed by a sixty-nine hour test. The oil temperature was maintained at 230 F., thejacket temperature at 180:F..:and the speed thereof was .maintained 'at1,800 R. P. M. At the end .of the test p the .amount .of port .closure was :determined 65 seconds :at 210 and containing 0.17 per cent Table 5 of Nuodex. The results of these tests are tabu- V lated below In Table Improving Agent 1 PS1? Port Table 4 ,by Wt. Clogging- None :30 Improving Agent, i rgf fi'it N i N. t Time, l ji s sf Product one u 33 byWt. Hrs Mgins. V c

.It will be'apparentiromthe foregoing-that. the NW 2 t-"g it reaction products ofthisinvention areqoutstand 1:0 15 03003 ingfor usejin mineral oils. The amount *Oflimw g provingagentused-may be varieddepending-um 1, 03778) on the *mineral oil or mineral oilfraction with which it is blended and the properties desiredin go the final oil composition. The acidic reaction It W111 be apparenttfmm results presented products, and metalsaltsthereof, may be used in a 4 ha l Three much.less efiec' amounts ranging from about T15 per cent to about tlve m i 'P i nearmg 1O ss .than Pmduct 5 .per cent and in-general compositionsof the Two, which is 6.11 ec tly compai ative therew th. it desired improved properties may be Obtained W be noted h *Jmduct ThrLee was h actel' with these materials in amounts ,of from. about ized by a hearing loss of almost seven times that Tlgper cent to about 2 per cent 7 e hlrd which P t .ItJS-tO be understood-that this invention is h f t Thls 1S evldfnce d1 eren not to be construed vas limited to theforegoing kind oi' acti o n possessedby p ofducts of tile type illustrative examples :but is to be broadly rcom of 39 A slmLar erence m 13 :lo. struecl in the light of the language of the apexhibited by Product -rour when compared with pended claims i Product This application is a division of .copending ap- RING SrIcKiNe Tssr plication Serial Number 620,653, rfiled October :In'addition to the foregoing tests aitypical ;0il-

9 t f f i f i and'an oilblend thereof containing a representa- 1s of apphcatlon tiveimproving agent were subjected to a single- 1 i filed Y' 1943, With Orland cylinder C. F.-R.'Elflgllle Test, i. e., actual engine HOWPatBHtINO- 2385,207- operating conditions. The engine was operated 101mm: continuouslyv over a time interval of twenty-eight AS a Composition fan acid c hours, with'the cooling medium held at a temphosphorusand 'S reac ion peratureofabout 390 Rand at a speedorlnoc product ob ained y reac in one molar pr p r- R. P. M., which is equivalent to a road speed of tion of DhOSDhOFLlS Ema-Sulfide With aDD about-twenty-five miles per hour. The oiltemmately two molar p p s o a ChIOrO-WaX- perature was heldat'about l50Fxduring the test. P1181101, in t p e oof "a vFriodel-Crafts cat- The oil used in this test was a lubricating oil alyst t mp tur tw about 100 C. and stock of 120 seconds Saybolt Universal viscosity 2 (s. U. v.) at 210 F. and the conditions observed :AS a nevi/composition f ma er. an acidic at the end of the test were: (A) the extent to p p and u -w a react on which the piston rings were stuck; (B) the extent product obtained y reacting e m r p opwto which the slots in the oil rings were filled with tion, f p sphorus pentasulfide with app deposit; ((3) the amount of carbonaceous deposits mately o 91 plopo tionsof a chloro-waxon the piston; and (D) the acidity or neutralizaphenol, at a temperature between about 100 C. tion number (N. N.) of the oil at the end of the and about 200 C., vand .treating the reaction test. The results of this test are Presented below mixture thus formed with a small amount of in Table 5. finely divided zinc and water.

Table 5 Ring Condition Degrees Stuck Slots Filled gg ggg N. N.

None .360 360 ,360 .360 ,360 .60 so .20 11.7 2. 3 ProductOno 0:67 0 0 0 0 0 0 -0 O 659:- 1'14 DIESEL Enema OPERATION "3. As a new composition of matter, an acidic A-single-cylinder General Motors Diesel engine phosphorus and 5111fur "C0ntaining c wasrun with a twelve hour break-in period folproduct Obtamed by Yeactlng one molar D P tion of phosphorus pentasulfide with approximately .two .molar proportions of a chloro-waxphenol in the presence of a 'F-riedel-Cra'fts zacat alyst, rat a temperature between about and:aloout.'200:C.. and.treatingithe.reaotionamixture thus formed with a small amount of finely divided zinc and water.

4. As a new composition of matter, an acidic phosphorusand sulfur-containing reaction product obtained by reacting one molar proportion of phosphorus pentasulfide with a paraflin chloro-wax-substituted phenol containing approximately two molar proportions of phenol in the presence of aluminum chloride, at a temperature between about 100 C. and about 200 C., and treating the reaction mixture thus formed with a small amount of zinc dust and water.

5. The method of making an acidic, phosphorusand sulfur-containing reaction product of a chloro-wax-phenol, which comprises: reacting one molar proportion of phossphorus pentasulfide with approximately two molar proportions of a chloro-wax-phenol in the presence of a Friedel-Crafts catalyst, at a temperature between about 100 C. and about 200 C., to form a reaction mixture containing said reaction product; and separating said reaction product from said reaction mixture.

6. The method of making an acidic, phosphorusand sulfur-containing reaction product of a chloro-wax-phenol, which comprises: reacting one molar proportion of phosphorus pentasulfide with approximately two molar proportions of a chloro-wax-phenol, at a temperature between about 100 C. and about 200 C., to form a reaction mixture containing said reaction product; treating said reaction mixture with a small amount of finely divided zinc and water; and separating said reaction product from the reaction mixture formed in the last-mentioned operation.

7. The method of making an acidic, phosphorusand sulfur-containing reaction product of a chloro-wax-phenol, which comprises: reacting one molar proportion of phosphorus penta- 10 sulfide with approximately two molar proportions of a chloro-wax-phenol in the presence of a Friedel-Crafts catalyst, at a temperature between about 100 C. and about 200 0., to form a reaction mixture containing said reaction prodnot; treating said reaction mixture with a small amount of finely divided zinc and water; and separating said reaction product from the reaction mixture formed in the lastmentioned operation.

8. The method of making an acidic, phosphorusand sulfur-containing reaction product of a paralfin wax-substituted phenol, which comprises: reacting one molar proportion of phosphorus pentasulfide with a paraffin chlorowax-substituted phenol containing approximately two molar proportions of phenol in the presence of aluminum chloride, at a temperature between about 100 C. and about 200 C., to form a reaction mixture containing said reaction product; treating said reaction mixture with a small amount of zinc dust and water; and separating said reaction product from the reaction mixture found in the last-mentioned operation.

HARRY J. ANDRESS, JR.

REFERENCES CITED The following references are of record in the file of this patent:

Giammaria Nov. 5, 1946 Certificate of Correction Patent No. 2,537,926 January 9, 1951 HARRY J. ANDRESS, JR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 69, for l 3 per cent read 1.3 per cent;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 14th day of August, A. D. 1951.

THOMAS F. MURPHY,

Assistant Gonunim'mwr of Patents. 

1. AS A NEW COMPOSITION OF MATTER, AN ACIDIC PHOSPHORUS- AND SULFUR-CONTAINING REACTION PRODUCT OBTAINED BY REACTING ONE MOLAR PROPORTION OF PHOSPHORUS PENTASULFIDE WITH APPROXIMATELY TWO MOLAR PROPORTIONS OF A CHLORO-WAXPHENOL, IN THE PRESENCE OF A FRIEDEL-CRAFTS CATALYST AT A TEMPERAPTURE BETWEEN ABOUT 100* C. AND ABOUT 200* C. 